Reshapable hair styling composition comprising silicon-containing polycondensates

ABSTRACT

A reshapable hair styling composition comprising at least one silicon-containing polycondensate chosen from polyurethanes, polyureas, and polyurethane-ureas, such as a polycondensate that is functionalized with at least one hydrolyzed or hydrolyzable silyl group, wherein said composition provides a reshapable effect.

The present invention relates to a reshapable hair styling composition.

Fixing the hairstyle is an important element in hair styling, andinvolves maintaining a shaping that has already been carried out, orsimultaneously shaping and fixing the hair.

In accordance with the invention, the term “hair styling composition”relates to any kind of hair composition that can be used to effect hairstyling, for example fixing compositions, shampoos, conditioners,permanent waving compositions, hair care products, and hair treatmentproducts.

The most prevalent hair styling compositions on the cosmetic market forshaping and/or maintaining the hairstyle are spray compositionscomprising a solution, usually alcohol- or water-based, and one or morematerials, generally polymer resins. One of the functions of polymerresins is to form links between the hairs, these materials also beingcalled fixatives, in a mixture with various cosmetic adjuvants. Thissolution is generally packaged either in an appropriate aerosolcontainer, which is pressurized with the aid of a propellant, or in apump flask.

Other known hair styling compositions include styling gels and mousses,which are generally applied to the wetted hair before brushing orsetting it. In contrast to the conventional aerosol lacquers, thesecompositions have the disadvantage that they do not allow the hair to befixed in a shape created before their application. In fact, thesecompositions are essentially aqueous and their application wets the hairand is therefore unable to maintain the initial shape of the hairstyle.In order to shape and fix the hairstyle, therefore, it is necessary tocarry out subsequent brushing and/or drying.

Such hair styling compositions all have the same disadvantage that theydo not allow the hairstyle to be later modified to a desired shape,which is other than that formed initially, without starting the stylingand fixing operations again. Moreover, under various kinds of stress,the hairstyle has a tendency to take on an undesirable permanent set,which cannot easily be modified. Also in the styling process, onedesires hair conditioning benefits, such as ease of combing and softhair feel appearance.

A subject of the invention is a reshapable hair styling compositioncomprising at least one silicon-containing polycondensate chosen frompolyurethanes, polyureas, and polyurethane-ureas, wherein saidcomposition provides a reshapable effect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one silylated polycondensate chosen frompolyurethanes, polyureas, and polyurethane-ureas, wherein saidcomposition provides a reshapable effect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one siliconated polycondensate chosenfrom polyurethanes, polyureas, and polyurethane-ureas, wherein saidcomposition provides a reshapable effect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one polycondensate that isfunctionalized with at least one group chosen from hydrolyzed silylgroups and hydrolyzable silyl groups, wherein said at least onepolycondensate is the product of reactants comprising:

(a) at least one isocyanate terminated polycondensate prepolymer, whichis the product of reactants comprising

(i) at least one polyisocyanate and

(ii) at least one polyol;

(b) at least one polyfunctional chain extender;

(c) at least one silyl containing component; and

(d) at least one hydrophilic component,

wherein said composition provides a reshapable effect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one silicon-containing polycondensatechosen from polyurethanes, polyureas, and polyurethane-ureas, such as asilylated polycondensate, a siliconated polycondensate, or apolycondensate that is functionalized with at least one group chosenfrom hydrolyzed silyl groups and hydrolyzable silyl groups, as describedabove, wherein said reshapable hair styling composition is in the formof a spray, aerosol, mousse, gel, stick, mud, or lotion.

Another subject of the invention is an aerosol device comprising avessel, which comprises: (1) an aerosol composition, which provides areshapable effect and comprises a liquid phase comprising at least onecomposition comprising at least one silicon-containing polycondensatechosen from polyurethanes, polyureas, and polyurethane-ureas, such as asilylated polycondensate, a siliconated polycondensate, or apolycondensate that is functionalized with at least one group chosenfrom hydrolyzed silyl groups and hydrolyzable silyl groups, as describedabove, and a propellant, and (2) a dispenser.

Another subject of the invention is a method of cosmetically treatinghair, comprising applying to the hair before, during, or after shapingof a hairstyle of said hair a composition comprising at least onesilicon-containing polycondensate chosen from polyurethanes, polyureas,and polyurethane-ureas, such as a silylated polycondensate, asiliconated polycondensate, or a polycondensate that is functionalizedwith at least one group chosen from hydrolyzed silyl groups andhydrolyzable silyl groups, as described above, wherein said compositionprovides a reshapable effect.

Another subject of the invention is a method of reshaping hair,comprising: (1) applying to the hair before, during, or after theinitial shaping of the hairstyle, a composition comprising at least onesilicon-containing polycondensate chosen from polyurethanes, polyureas,and polyurethane-ureas, such as a silylated polycondensate, asiliconated polycondensate, or a polycondensate that is functionalizedwith at least one group chosen from hydrolyzed silyl groups andhydrolyzable silyl groups, as described above, wherein said compositionprovides a reshapable effect, and (2) thereafter shaping the hairstyleat least once, wherein no additional composition or heat is added.

In one embodiment of the invention, such reshapable hair stylingcompositions may be in the form of a dispersion. The term “dispersion”means generally a two phase system where one phase contains discreteparticles distributed throughout a bulk substance, the particles beingthe disperse or internal phase, and the bulk substance being thecontinuous or external phase. The continuous phase may be an aqueousphase and at least a portion of the polymer may exist as discreteparticles. Dispersions are possible through the use of certaincomponents that are insoluble in the aqueous system. By “dispersion,” itis also meant that not necessarily the entire polymer needs to be waterinsoluble; some of the polymer can be soluble in the water mixture. Itmay be desirable that a dispersion remains stable under ambientconditions. In one embodiment, dispersions are stable at roomtemperature for more than 30 days, such as for more than 90 days, formore than 180 days, and for more than 360 days.

The phrase “silicon-containing polycondensate” means a polycondensatewith at least one silicon atom present anywhere within thepolycondensate. The silicon atom can be joined to any other atom. Theterm “hydrolyzable silyl group” means generally a silicon atomsubstituted with at least one moiety that will react with water to givea hydrolyzed silyl group. The term “hydrolyzed silyl group” meansgenerally a silicon atom substituted with at least one —OH moiety. Theinventors recognize that at some time after formation of apolycondensate that is functionalized with at least one group chosenfrom hydrolyzed silyl groups and hydrolyzable silyl groups, such asduring the drying of the polymer, one or more —OH moieties may reactfurther, such as, for example, forming an ≡Si—O—Si≡ group. Such productsare encompassed within the phrase “polycondensate that is functionalizedwith at least one group chosen from hydrolyzed silyl groups andhydrolyzable silyl groups.” A polycondensate that is functionalized withat least one silyl group, whether or not hydrolyzed or hydrolyzable, isalso referred to as a silylated polycondensate in this document and suchsilylated polycondensates are a sub-genus of silicon-containingpolycondensates. The at least one silyl group, whether or not hydrolyzedor hydrolyzable, may be terminal to and/or pendant from thepolycondensate. The phrase “siliconated polycondensate” means apolycondensate containing necessarily at least one ≡Si—O—Si≡ group.Siliconated polycondensates are a subgenus of silicon-containingpolycondensates.

The term “reshapable” hair styling composition means a hair stylingcomposition providing hair styling that can be restored or modifiedwithout new material or heat being applied. For example, in order torestore or modify the hairstyle in case of “drooping” or loss of setting(dishevelment), no new materials, such as water or any form of fixingagent, or heat are required. Thus, to provide a “reshapable” effectmeans to provide a hair styling that can be restored or modified withoutnew material or heat being applied. The efficacy of the composition canbe long lasting, such as 10-24 hours, giving rise to a durable stylingeffect. Other terms, which may be synonymous with reshapable, includerepositionable, remoldable, restyleable, rearrangable, and remodelable.

Various aqueous polycondensate dispersions comprising at least onehydrolyzable or hydrolyzed silyl group have been prepared by thoseskilled in the art. For example, U.S. Pat. Nos. 3,941,733; 3,983,291;5,554,686; 5,756,633; 5,919,860; 5,952,445; 6,046,295; and 6,111,010,whose disclosures are incorporated herein in their entirety, disclosepreparations of water-dispersed polyurethane-urea polycondensatesterminated with silane functionality suitable for use as coatings forleather, paper, wood, metals, ceramics, stone, concrete, straw, glass,porcelain, textiles, and plastics, and for use as binders, adhesives,and impregnants. U.S. Pat. No. 4,567,228, whose disclosure isincorporated herein in its entirety, discloses aqueous dispersions ofinternally (i.e. pendant) silylated polycondensates and their use ascoatings on hydroxyl-containing surfaces. U.S. Pat. No. 5,041,494, whosedisclosure is incorporated herein in its entirety, discloses aqueousdispersions of polycondensates that have terminal and/or pendant silanefunctionality for use as a coating composition on organic or inorganicsubstrates including glass, wood, metals, plastics, leather, paper,building materials, stone and rock.

Although aqueous dispersions of silylated polycondensates of theinvention have been widely disclosed, the inventors are not aware of anyreferences to their use in reshapable hair styling compositions.

Processes and starting materials for preparing silylated polycondensatesof the invention are disclosed in the references cited above. Suitablecomponents for preparing the silylated polycondensates includepolyisocyanates (such as diisocyanates); high molecular weightcomponents (such as a polyol); low molecular weight chain extenderscontaining hydroxy, hydrazide, or amine groups; compounds containingionic or nonionic hydrophilic groups; and compounds containing silylgroups. Chain terminators can optionally be included to controlmolecular weight and reduce cross-link density in the final polymer.Each component is discussed below in detail.

Another exemplary method for preparing a silylated polycondensate of theinvention involves reacting at least one polyisocyanate with at leastone polyol to form at least one isocyanate-terminated polycondensateprepolymer. The prepolymer can be chain extended followed by reactionwith at least one compound containing silyl groups to form the silylatedpolycondensate. Additionally, the silylated polycondensate may bedispersed in a solvent through the use of external surfactants or byincorporating a hydrophilic group into the polymer. The resultingpolymers may then be used to formulate various reshapable hair stylingcompositions.

As disclosed in U.S. Pat. No. 3,941,733, use of a distinctpolyfunctional chain extender is not necessary to produce silylatedpolyurethane polycondensates. In some embodiments, the at least onehydrophilic component or the at least one silyl containing component mayalso function as the at least one polyfunctional chain extender.

Polyisocyanate Component

Any suitable organic polyisocyanate, including aliphatic,cycloaliphatic, arylaliphatic, and aromatic polyisocyanates, can be usedalone or in combination to produce silicon-containing polycondensates ofthe invention, such as silylated polycondensates. While aromatic oraliphatic polyisocyanates are suitable, the aliphatic polyisocyanatesmay yield softer polymers and coatings that may have better lightstability than the aromatic polyisocyanates. In one embodiment, the atleast one polyisocyanate is a diisocyanate. Low levels ofpolyisocyanates containing more than two isocyanate groups in themolecule can be included without measurable changes in thecharacteristics of the resulting polymer.

In another embodiment, the at least one polyisocyanate may be chosenfrom dicyclohexylmethane 4,4′-diisocyanate (commonly referred to asH₁₂MDI), 1,3-bis(isocyanatomethyl) cyclohexane,1,3-bis(1-isocyanato-1-methylethyl) benzene (commonly referred to asTMXDI), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethyl cyclohexane(commonly referred to as isophorone diisocyanate or IPDI), m-phenylenediisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 4,4′-diisocyanato diphenylmethane (commonlyreferred to as MDI), benzidine diisocyanate,naphthalene-1,5-diisocyanate, hexamethylene diisocyanate (commonlyreferred to as HDI) and other alkylene diisocyanates (e.g.,tetramethylene diisocyanate, decamethylene diisocyanate, anddodecamethylene diisocyanate), 4,4′,4″-triphenylmethane triisocyanate,polyphenylmethylene polyisocyanates that are produced by phosgenation ofaniline/formaldehyde condensation products containing up to about fouraromatic rings, dianisidine diisocyanate, xylene diisocyanate,bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)cyclohex-4-ene-1,2-dicarboxylate, and bis(2-isocyanatoethyl) carbonate.

Polyol Component

In producing a silicon-containing polycondensate of the invention, suchas a silylated polycondensate, at least one polyhydroxy compound, orpolyol, may be used in a reaction with the at least one polyisocyanate,as described above.

In one embodiment, the at least one polyhydroxy compound may be chosenfrom (a) lactone polyols and alkylene oxide adducts thereof, (b)polyester polyols, and alkylene oxide adducts thereof, (c)polyoxyalkylene polyols, polyoxycycloalkylene polyols, and alkyleneoxide adducts thereof, and (d) polytetramethylene glycols.

In another embodiment, the at least one polyol component may be chosenfrom diols. The term “diol” is intended to include mixtures of diols aswell as mixtures containing low levels of triols or tetrols that do notexcessively affect the properties of the final product. Exemplary diolsmay be chosen from polyester diols and polyoxyalkylene diols.

The term “alkylene oxide” includes, e.g., ethylene oxide,1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, isobutylene oxide,epichlorohydrin, and the like and mixtures thereof.

Lactone polyols may be prepared by reacting a lactone, such asepsilon-caprolactone or a mixture of epsilon-caprolactone and analkylene oxide, with a polyfunctional initiator such as a polyhydricalcohol. The term “lactone polyols” also includes the various copolymerssuch as lactone copolyesters, lactone polyester/polycarbonates, lactonepolyester/polyethers, lactone polyester/polyether/polycarbonates, andthe like.

Polyester polyols are esterification products that range from liquids tonon-crosslinked solids, i.e., solids that are soluble in many of themore common inert normally liquid organic media. Polyester polyols maybe prepared by the reaction of polycarboxylic acids, their anhydrides,their esters, or their halides, with a stoichiometric excess of apolyol. Exemplary polycarboxylic acids that can be used to prepare apolyester polyol may be chosen from dicarboxylic acids and tricarboxylicacids, such as maleic acid, succinic acid, glutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid,1,2,4-butane-tricarboxylic acid, phthalic acid, and the like.Esterification reactions are well known in the art.

Polyoxyalkylene polyols may be chosen from alkylene oxide adducts of,e.g., water, ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol, glycerol, 1,2,6-hexanetriol, 1,1,1-trimethylolethane or propane, pentaerythritol, and the like. The alkylene oxidesused in producing polyoxyalkylene polyols normally have from 2 to 4carbon atoms. In one embodiment, the alkylene oxide is chosen fromethylene oxide, propylene oxide, and mixtures thereof.

Another useful class of polyols is the polyoxytetramethylene glycols,which may be prepared by polymerizing tetrahydrofuran in the presence ofan acidic catalyst.

The molecular weight of the at least one polyol component may be onesignificant factor in determining the final properties of the polymer.Generally, the higher the molecular weight, the softer the resultingpolymer. The term “molecular weight” is used herein to refer to thenumber average molecular weight (M_(n)). In one embodiment, polyols ofmolecular weight as low as 200 and as high as 5000 may produce suitablesilicon-containing polycondensates of the invention, for examplesilylated polycondensates, such as polyols with a molecular weightranging from 300 to 3000, which are readily commercially available.Polyols of lower molecular weight can be used as the at least onepolyfunctional chain extender as discussed below.

Polyfunctional Chain Extender Component

As used herein the term “polyfunctional chain extender” means apolyactive hydrogen compound having a functionality of about 2 to about4, such as from about 2 to about 3, and further such as about 2 andgenerally having a molecular weight ranging from about 30 to about 2000,such as from about 30 to about 1000.

In one embodiment, the at least one polyfunctional chain extender may bechosen from polyfunctional alcohols, amines, and carboxylic acidhydrazides. In another embodiment, the at least one polyfunctional chainextender may be chosen from polyfunctional amines and carboxylic acidhydrazides. Useful polyamines may include ethylenediamine,1,6-diaminohexane, piperazine, tris(2-aminoethyl)amine, and amineterminated polyethers such as JEFFAMINE D230 and JEFFAMINE D400, fromthe Huntsman Corporation, Salt Lake City, Utah, USA. Useful carboxylicacid hydrazides may include adipic acid dihydrazide and oxalic aciddihydrazide. Useful polyfunctional alcohols may include alkylene diolshaving 2 to 24 carbon atoms such as ethylene glycol, diethylene glycol,1,4-butane diol, 1,8-octane diol, and 1,2-decandiol.

Other useful chain extenders may include polythiols such as1,2-ethanedithiol, 1,4-butanedithiol, 2,2′-oxytris(ethane thiol), anddi- and tri-mercaptopropionate esters of poly(oxyethylene) diols andtriols. Water may also be useful as a polyfunctional chain extender asit reacts with isocyanate to form an unstable carbamic acid, which losescarbon dioxide to liberate an amine. This amine is then available toreact with another isocyanate.

Hydrophilic Component

In one embodiment, the silicon-containing polycondensate of theinvention, such as a silylated polycondensate, may be dispersed in asolvent through the use of external surfactants or by incorporating ahydrophilic group into the polymer. The latter may be achieved using atleast one hydrophilic component having at least one water solubilizinggroup and at least one isocyanate reactive functional group. The atleast one hydrophilic component may act to stabilize the polycondensatedispersion in an aqueous solvent system. Suitable hydrophilic componentsmay be chosen from groups that contain an ionic group, groups thatcontain at least one moiety capable of forming an ionic group, andgroups that contain nonionic water-soluble groups such as polyethyleneglycol and its copolymers with propylene glycol.

When present, the ionic group of the at least one hydrophilic componentcan be cationic, anionic, or zwitterionic. The cationic groups mayoriginate from the at least one isocyanate or the at least one polyolcomponent but most conveniently are added in as the at least one polyolcomponent. In one embodiment, the cationic group may be incorporateddirectly into the prepolymer. For example, a quaternary diol such asVARIQUAT 1215 may be reacted into the prepolymer directly. In analternative embodiment, a precursor group may be reacted into theprepolymer and then may be rendered cationic in a subsequent reaction.For example, active hydrogen functional tertiary amines such asmethyldiethanolamine and its polyethoxylated adducts may be incorporatedinto the prepolymer backbone and subsequently protonated with a mineralor organic acid to form an ionic salt or alkylated to form a quaternaryammonium group. The reaction of the incorporated tertiary amine withhydrogen peroxide, propane sultone, or lactone is one method that mayyield suitable zwitterionic moieties.

In one embodiment, stabilizing cationic components may be water soluble,i.e., generally having a solubility in water of at least 1% by weight,such as in excess of 10% by weight. Such stabilizing cationic compoundsmay have the following structure:

R¹—N⁺(R²)[(CH₂CH₂O)_(n)H]₂X⁻

where

R¹ is a group chosen from C₁ to C₁₈ alkyls, C₆ to C₁₈ aryls, and C₆ toC₁₈ arylalkyls optionally substituted in and/or on the chain by at leastone atom chosen from N, O, and S atoms;

R² is a group chosen from a hydrogen atom and C₁ to C₁₈ alkyls;

n is an integer ranging from about 1 to about 200, such as from about 1to about 50 and further such as from about 1 to about 20; and

X⁻ is chosen from halides, sulfates, methosulfates, ethosulfates,acetates, carbonates, and phosphates.

In one embodiment, cationic stabilizing compounds may be chosen fromprotonated and alkylated methyl diethanol amines as well as PEG 2cocomonium chloride and PEG-15 cocomonium chloride available fromCKWitco, Greenwich, Conn., USA as VARIQUAT 638 and VARIQUAT K1215respectively.

It is possible to incorporate cationic compounds that have a singlereactive hydrogen group.

In one embodiment, the anionic stabilizer may be present on either theat least one isocyanate component or the at least one polyol component.In another embodiment, the anionic group may be chosen from sulfonates,phosphonates, phosphates, and carboxylates, such as for example fromsulfonates and carboxylates, and further such as, for example, fromsulfonates. The sulfonates may be chosen from the sulfonated polyolsdescribed in U.S. Pat. No. 4,738,992 (Larson et al.), whose disclosureis incorporated herein in its entirety by reference. In one embodiment,the sulfonate may be chosen from polyesterdiols having the followingstructure:

wherein M is a cation chosen from H, Na, K, Li, alkaline earth metals,and primary, secondary and tertiary ammonium cations, such as ammonium,methylammonium, butylammonium, diethylammonium, triethylammonium,tetraethylammonium, and benzyltrimethylammonium cations; each R³isindependently chosen from divalent aliphatic groups having an averagemolecular weight ranging from about 200 to about 600 and comprising atleast one ether and/or ester functional group, which may be chosen from:

—CH₂CH₂—(OCH₂CH₂—)_(n)—,

—CH(CH₃)CH₂—(OCH(CH₃)CH₂—)_(n)—,

—(CH₂)₄—(O(CH₂)₄)_(n)—, and

—(CH₂)_(m)CO—[O(CH₂)_(m)CO]_(n)— groups;

where m is an integer ranging from about 2 to about 5 and n is aninteger ranging from about 2 to about 15.

Suitable carboxylate and carboxylic acid functional polyols may includepolyols chosen from dimethylolpropionic acid and its polyethoxylatedderivatives as well as acid grafted polyethers such as the UCARMODpolyols available from Union Carbide Specialty Chemicals Div., Danbury,Conn. Carboxy functional polyamines, such as lysine and histidine mayalso be useful. In one embodiment, these polyols can be neutralized withan organic or inorganic base either before or after preparation of theat least one isocyanate terminated polycondensate prepolymer.

In one embodiment, the addition of an external surfactant to thepolycondensate is used instead of or in combination with theincorporation of a hydrophilic group into the polymer. Suitablesurfactants may be chosen from cationic, anionic, nonionic, andamphoteric (such as zwitterionic) surfactants. The surfactants may bepresent in an amount sufficient to disperse the silicon-containingpolycondensate of the invention, such as a silylated polycondensate, ina solvent, including water.

Silyl Containing Component

At least one silyl group may be incorporated into the polycondensate ofthe invention terminally (at the ends) and/or internally (pendant fromthe backbone). When incorporated terminally, a component containing atleast one silyl group and at least one electrophilic or nucleophilicreactive group may be used. For example, a prepolymer terminated withisocyanate can be reacted with a silane functionalized with an alkylamine, hydroxyl, or thiol. Suitable silanes that may react withisocyanates may be chosen from, but are not limited to, the followingcompounds:

H₂NCH₂CH₂CH₂Si(OC₂H₅)₃,

HN(CH₂CH₂CH₂Si(OC₂H₅)₃)₂,

HSCH₂CH₂CH₂Si(OCH₃)₃,

HO(C₂H₄O)₃C₂H₄N(CH₃)(CH₂)₃Si(OC₄H₉)₃,

H₂NCH₂C₆H₄CH₂CH₂Si(OCH₃)₃,

HSCH₂CH₂CH₂Si(OCOCH₃)₃,

H₂NCH₂CH₂CH₂Si(OCH₃)₃,

HN(CH₃)CH₂CH₂Si(OCH₃)₃, and

HSCH₂CH₂CH₂SiCH₃(OCH₃)₂.

Conversely, a prepolymer terminated with an amine or a hydroxyl moietycan be reacted with a component containing a silane that isfunctionalized with an alkyl isocyanate such as3-isocyanatopropyltriethoxysilane, and OCNCH₂CH₂CH₂Si(OCH₃)₃.

When incorporated internally, a component containing at least one silylgroup and at least two isocyanate or isocyanate reactive groups may beused. For example, silanes functionalized with two hydroxyls or twoamines may be used as both the at least one silyl containing componentand the at least one chain extender, placing silane functionalityinternally. In one embodiment, silane that is functionalized with analkyl isocyanate with two reactive sites may be chosen from:

(HOC₂H₅)₂NC₃H₆Si(OCH₃)₃, and

H₂NCH₂CH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃.

A silane with only one electrophilic or nucleophilic group can be used,provided that the polymer possesses a companion nucleophilic orelectrophilic group along its backbone. For example, a pendantcarboxylic acid functionality on the polymer chain may be reacted withan alkyl epoxy silane such as 3-glycidoxypropyltrimethoxysilane.

Other methods of incorporating silyl groups are known in the art, suchas hydrosilation of a pendant or terminal olefin with a trialkoxysilanehydride.

Silane compounds containing two or three hydrolyzable groups on thesilicon atom (as X₂Si═ or X₃Si—) and one or two organic groups aresuitable for forming the silyl groups. The “X” can be any of theconventional hydrolyzable groups, such as hydrogen, alkoxy, acyloxy,halogen, amino, oxime, and the like.

In one embodiment, a silane compound containing one or no hydrolyzablegroups on the silicon atom may be suitable for forming the silyl groups;however, such compounds often lack commercial availability, have slowerreactivity, and lower cross-linking efficiency than silane compoundscontaining two or three hydrolyzable groups on the silicon atom.

In one embodiment, the silane compound may be chosen from those with thestructure:

(R⁴O)₃SiR⁵Z,

wherein (R⁴O)₃SiR⁵— is a silyl moiety; R⁴ is a radical chosen from C₁ toC₄ alkyls, such C₁ to C₂ alkyls (i.e., methoxy, ethoxy), and C₂ to C₅acyls, such as C₂ to C₃ acyls (i.e., acetyl or propionyl); R⁵ is radicalchosen from divalent C₂ to C₂₀ organic bridging radicals, such as C₃ toC₁₀ organic bridging radicals, wherein the organic bridging radicals arechosen from (1) divalent hydrocarbyl radicals and free fromisocyanate-reactive groups, (2) divalent oxyalkylene radicals, such asmono- or poly-oxyalkylene radicals containing not more than one etheroxygen per two carbon atoms, and (3) divalent hydrocarbylamino radicals.Z is either a nucleophilic group such as —OH, —SH, —NHR, —NH₂, and—N(C₂H₄OH)₂ or an electrophilic group such as —NCO and epoxide.Representative divalent organic radicals include —CH₂CH₂—, —CH ₂CH₂CH₂—,—CH₂CH₂CH₂OCH₂CH₂—, —CH₂CH₂CH₂NHCH₂CH₂—, and —CH₂CH₂C₆H₄CH₂CH₂—. Suchsilicon-containing compounds are well known in the art and many arecommercially available or are readily prepared.

While not being limited to theory, it is believed that a chain-extendedsilylated polycondensate of the invention may be cured by hydrolysis ofthe silyl group and formation of siloxane linkages. This reactionprobably may begin as soon as the polymer is exposed to water, butgenerally proceeds slowly at room temperature and within a pH range ofabout 6.5 to about 9. The reaction proceeds more rapidly after dryingand is accelerated in the presence of acidic or basic catalysts. Theformation of siloxane linkages crosslinks the film formed from thepolymer. These crosslinks are distinguished from crosslinks andbranching that may form in low concentration from the use of triols,triisocyanates, tetrols, and other highly functional reactants inpreparing the prepolymer. The latter crosslinks are herein sometimesreferred to as prepolymer-derived crosslinks and are to be understood asthe type of crosslinks present before curing.

Chain Terminator Component

As used herein the term “chain terminator” means an active hydrogencompound having a functionality of about 1 and generally having a numberaverage molecular weight ranging from about 30 to about 2000, such asfrom about 30 to about 1000. In one embodiment, a chain terminatorcomponent may be included during preparation of the prepolymer or addedduring the dispersion and chain extension steps. Chain terminators maybe chosen from monofunctional alcohols, amines, and carboxylic acidhydrazides. When chain termination is done during the dispersion step,the chain terminator may be chosen from monofunctional amines, becausethe isocyanate functional moieties will selectively react with them inthe presence of water. Useful amines include butyl amine and2-amino-2-methyl-1-propanol. Useful monofunctional alcohols includethose having 2 to 24 carbon atoms such as ethanol, butanol, octanol,cetyl alcohol, and stearyl alcohol.

Dispersion Techniques

Aqueous dispersions of some silicon-containing polycondensates of theinvention may be prepared in accordance with the methods known inpolyurethane chemistry and described, e.g., in “WaterbornePolyurethanes,” Rosthauser et al, Advances in Urethane Science andTechnology, Vol. 10, pg. 121-162 (1987), whose disclosure isincorporated by reference in its entirety herein.

These methods generally involve subjecting the silicon-containingpolycondensate to a high shear process in the presence of an aqueouscarrier. Microfluidization is one such process for making stable uniformsub-micron dispersions, including dispersions of silicon-containingpolycondensate. The process uses high-pressure liquid jet milling tocombine water dispersible polymers with water. In one embodiment, thesilylated polycondensate of the invention has a viscosity in the rangeof 1 to 500,000 centipoises as measured by a standard Brookfieldviscometer with an appropriate spindle and speed to achieve a readingbetween 20-80 at a room temperature of about 25° C. When higherviscosity is encountered, an organic solvent may be added to reduce theviscosity to the desired range. In the microfluidization process, thesilicon-containing polycondensate or a solution of silicon-containingpolycondensate in an organic solvent can be injected into a water streamand then subjected to high pressure of 0.6 to 300 MPa (100 to 40,000psi) liquid jet milling in interaction chambers. The interactionchambers, which provide a high shear zone, are generally configured tobe explosive expansion chambers, or use high velocity impinging streams,or contain orifices in series having decreasing diameters. In thisprocess, all of the liquid is forced through the interaction chamberconfigurations providing uniform shear for all the material.

When organic solvent is used to aid in preparation of thesilicon-containing polycondensate and reduce viscosity, this solvent maybe miscible with water allowing for dispersion into an aqueous solution.If an organic solvent having a boiling point lower than 100° C. has beenused, the organic solvent may be evaporatively removed to leave anessentially aqueous polymer dispersion of the silicon-containingpolycondensate. Representative organic solvents useful for this processmay be chosen from acetone, methyl ethyl ketone, and tetrahydrofuran. Anorganic solvent that has a boiling point greater than 100° C. (referredto as “high boiling solvent” for convenience) can also be used. Whenused, the preparation should be conducted in as concentrated solution aspossible, e.g., preferably equal to or less than 20 weight percentsolvent to minimize the amount present in the dispersion. Such highboiling solvents should be chosen from materials that do not havetoxicity or irritancy concerns in cosmetic applications. Of course,solvents with boiling points lower than 100° C., such as ethanol, canoptionally be included in the final formulation to provide benefits suchas fast-drying.

According to one process for preparing a silylated polyurethane-ureadispersion, at least one isocyanate-functional prepolymer is prepared,chain extended and/or chain terminated to form a silylatedpolyurethane-urea and subsequently dispersed in water. This process isdisclosed in U.S. Pat. No. 3,479,310, whose disclosure is incorporatedin its entirety herein by reference.

When amines are reacted with the at least one isocyanate-functionalprepolymer, either as chain terminators or chain extenders, one methodof preparing a dispersion is by dispersing the prepolymer in water andthen reacting the prepolymer with the amino group-containing compounds,which may be mixed with water either before, during, or after dispersingthe at least one isocyanate-functional prepolymer.

The amount of amino group-containing compounds to be used in accordancewith the present invention is dependent upon the number of isocyanategroups in the prepolymer. Generally, the ratio of isocyanate groups toamino groups ranges from 1.0:0.6 to 1.0:1.1, such as from 1.0:0.8 to1.0:0.98, on an equivalent basis.

The reaction between the at least one isocyanate-functional prepolymerand the amino group-containing compounds is generally conducted attemperatures ranging from about 5° C. to about 90° C., such as fromabout 20° C. to 80° C., and further such as from about 30° C. to 60° C.The reaction conditions are normally maintained until the isocyanategroups are essentially completely reacted.

In one embodiment, the final product is a stable, aqueous dispersion ofsilicon-containing polycondensate particles having a solids content ofup to about 60%, such as about 15% to about 60%, and further such asabout 30% to about 45% by weight. A dispersion is deemed stable so longas the discrete particles of the internal phase remain distributedthroughout the bulk substance (external phase). It is always possible,however, to dilute the dispersions to any minimum solids contentdesired. The average particle size of the silicon-containingpolycondensate of the invention generally may be below about 1.0 micron,such as about 0.001 to about 0.5 microns and further such as about 0.01to about 0.3 microns. The small particle size may enhance the stabilityof the dispersed particles and may also lead to films with high surfacegloss.

In one embodiment, the dispersions may be blended with other dispersionsor with other known additives such as fillers, plasticizers, pigments(such as carbon black), silica sols and other known leveling agents,wetting agents, antifoaming agents, and stabilizers.

In another embodiment, the silicon-containing polycondensate of theinvention is in a cosmetically acceptable vehicle. The appropriatecosmetically acceptable vehicle is adapted to the method of applicationselected. The vehicle preferably comprises an appropriate solvent,including water, to which may be added additives such as gelling agents,foaming agents, and silicones.

It is understood that the person skilled in the art will know how tochoose the additional additives and their amount in the compositionaccording to the invention, such as the constituents of the vehicle, soas not to adversely affect or substantially affect its reshapable hairstyling properties.

In yet another embodiment of the invention, the silicon-containingpolycondensate of the invention has a glass transition temperature (Tg)ranging from about −100° C. to about 15° C. According to the presentinvention, the Tg of the silicon-containing polycondensate is obtainedfollowing the application of the silicon-containing polycondensate in asimplex vehicle to a substrate and then drying. The glass transitiontemperature is determined by the Differential Scanning Calorimetricmethod (DSC).

The composition according to the invention may comprise at least oneother constituent, which is conventional in cosmetics, chosen frompreservatives; perfumes; active hair care agents; plasticizers; anionic,cationic, amphoteric (such as zwitterionic), and nonionic surfactants;hair conditioning agents such as silicone fluids, fatty esters, fattyalcohol, long chain hydrocarbons, emollients, lubricants, and penetrantssuch as lanolin compounds, protein hydrolysates, and other proteinderivatives; anionic, cationic, amphoteric (such as zwitterionic), andnonionic polymers; dyes; tints; bleaches; reducing agents; pH adjustingagents; sunscreens such as UV filters; and thickening agents.

The compositions according to the invention can be provided in any formknown from the prior art, which is appropriate for their application tothe hair, including in the form of a vaporizable composition such assprays and aerosols, mousse, gel, stick, mud, or lotion.

The composition may be in any of the conventional forms of cosmeticcomposition including, but not limited to, shampoos, hair rinses,permanent waving compositions, waving compositions, hair dyecompositions, hair straightening compositions, hair fixing products,hair styling gel products, products to use before or after a hair dyetreatment, products to use before or after a permanent waving treatment,hair straightening compositions, products to use before or after a hairstraightening treatment, and fixing foams.

The composition according to the invention may be vaporizable, forexample by a pump, or may be a pressurized aerosol composition. It maybe vaporizable by a dispensing valve controlled by a dispensing head,which in turn comprises a nozzle, which vaporizes the aerosolcomposition. A vaporizable composition according to the inventioncomprises an appropriate solvent. Advantageously, the appropriatesolvent comprises at least one solvent chosen from water and loweralcohols. In accordance with the invention, the term lower alcohol meansa C₁ to C₄ aliphatic alcohol, preferably ethanol.

When the vaporizable composition according to the invention is anaerosol composition, it additionally comprises an appropriate amount ofpropellant. The propellant comprises compressed or liquefied gases,which are normally employed for the preparation of aerosol compositions.Suitable gasses include compressed air, carbon dioxide, nitrogen, andgases, such as dimethyl ether, fluorinated or non-fluorinatedhydrocarbons, and mixtures thereof.

The present invention additionally provides an aerosol device comprisinga vessel comprising an aerosol composition, which comprises on the onehand a liquid phase (or juice) comprising at least one hair stylingmaterial as described above in an appropriate medium and on the otherhand a propellant, and a dispenser for dispensing said aerosolcomposition.

The present invention additionally provides a method of treatingkeratinous fibers, especially hair, in which the composition accordingto the invention as defined above is applied to the hair before, during,or after the shaping of the hairstyle.

The compositions according to the invention can be rinsed off or notrinsed off the hair.

The present invention additionally provides the use of a composition asdefined above in, or for the preparation of, a cosmetic reshapable hairstyling formulation.

The determination of whether a composition with a silicon-containingpolycondensate according to the invention can provide a reshapableeffect can be determined by an in vivo test.

Where the composition is in the form of a lotion, for example, the invivo test proceeds as follows. The hair of the model is washed and thendivided into two symmetrical portions, the right and the left sides. Thecomposition is applied to one side of the head of the model, while areference composition is applied to the other side of the head. Thereference composition may, for example, be chosen from water, anexisting commercial product, or another composition under study. Thehairdresser dries and styles both sides of the head. The two sides ofthe head are separately evaluated for the styling effect, the cosmeticproperties, and the reshapable effect. For example, once dried, the hairis brushed in different directions to remove the original styling. Thehair is then brushed to restore the original styling. The process ofremoving the styling, restoring the styling, and evaluating the successof restoring the styling is repeated at least one more time to determinewhether the composition is a reshapable hair styling composition. Areshapable hair styling composition permits (1) the original hairstyling to be restored after brushing and (2) the creation of a new hairstyling after brushing, which may also be restored after brushing. Ifthe composition to be evaluated is in another form, such as a shampoo orconditioner, the in vivo test can be appropriately modified by oneskilled in the art.

It is understood that the person skilled in the art would recognize thatnot all formulations would provide reshapable effect for all hair typesduring in vivo testing and will know how to formulate and evaluatereshapable hair styling composition in view of the various hairparameters, such as length (short versus long), diameter (thin versusthick), structure (curly versus straight), condition (oily, dry, ornormal); and whether the hair is colored, bleached, permed, orstraightened. Thus, in vivo testing may require testing on 10-20different individuals.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

The invention may be understood more clearly with the aid of thenon-limiting examples that follow, and which constitute an advantageousembodiment of the compositions in accordance with the invention.

EXAMPLES

Several reshapable hair styling compositions according to the inventionwere produced with different silicon-containing polycondensates.Percentages given are by weight, unless otherwise specified.Abbreviations and sources for the components used to manufacturesilicon-containing polycondensates of the invention are disclosed in theTable.

Components Manufacturer Acetone J. T. Baker, Inc., Phillipsburgh, NJButylamine Aldrich Chemical Co., Milwaukee, WI Dibutyltin dilaurate(DTDL) Aldrich Chemical Co., Milwaukee, WI Diethylene glycol AldrichChemical Co., Milwaukee, WI Ethylene glycol (EG) Aldrich Chemical Co.,Milwaukee, WI Isophorone diisocyanate (IPDI) Aldrich Chemical Co.,Milwaukee, WI Methyl ethyl ketone (MEK) J. T. Baker, Inc.,Phillipsburgh, NJ Polycaprolactone diol Tone 0201 ™ diol, Union Carbide,Dansbury, CT Polycaprolactone sodium sulfo Prepared according to Example29 of isophthalate (PCPSSIP) U.S. Pat. No. 5,929,160 TriethylamineAldrich Chemical Co., Milwaukee, WI 1,2-decanediol Aldrich Chemical Co.,Milwaukee, WI 1,6-diisocyanatohexane Aldrich Chemical Co., Milwaukee, WI2,2′-bis(hydroxymethyl)- Aldrich Chemical Co., Milwaukee, WI propionicacid 3-aminopropyltriethoxysilane Aldrich Chemical Co., Milwaukee, WI4,4′-diisocyanato Aldrich Chemical Co., Milwaukee, WIdicyclohexylmethane

1) Preparation of the Silicon-containing Polycondensates

Example 1

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of PCPSSIP (349.7 g and 0.47 mol, based on a hydroxylequivalent weight of 370 for the mixture), polycaprolactone diol (39.3g, 0.08 mol), ethylene glycol (69.9 g, 1.13 mol), diethylene glycol(23.9 g, 0.23 mol), IPDI (450.1 g, 2.03 mol), DTDL (0.90 g, 1.4 mmol),and MEK (502 g) was charged to a vessel equipped with stirring andheated to 80° C. After 4 hours, a solution of3-aminopropyltriethoxysilane (49.9 g, 0.23 mol) in MEK (473 g) was addedto the reaction mixture, which was maintained at 80° C. for anadditional 15 minutes. Water (975 g) was added to the reaction mixtureover a 15 minute period with vigorous stirring and MEK was subsequentlydistilled from the mixture under reduced pressure to produce adispersion (50% solids) of a silanol-terminated polyurethane-urea inwater.

Example 2

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of 1,2-decanediol (69.71 g, 0.40 mol), 1,6-diisocyanatohexane(102.94 g, 0.61 mol), DTDL (0.27 g, 0.4 mmol), and acetone (161 mL) washeated with stirring to 55° C. After 2 hours, PCPSSIP (125.8 g, 0.17 molbased on a hydroxyl equivalent weight of 370 for the mixture) was added,and the mixture was heated for 2 additional hours at 55° C. A solutionof 3-aminopropyltriethoxy silane (9.79 g, 0.044 mol) in acetone (144 mL)was added to the reaction mixture, which was maintained at 55° C. for anadditional 15 minutes. Water (500 mL) was added to the reaction mixtureover a 15 minute period with vigorous stirring and acetone wassubsequently distilled from the mixture under reduced pressure toproduce a dispersion of a silanol-terminated polyurethane-urea in water.Modulated differential scanning calorimetry (MDSC) analysis made of afilm of the dispersion indicated that the polymer had a T_(g) of −17° C.

Example 3

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of 1,2-decanediol (34.86 g, 0.20 mol), 1,6-diisocyanatohexane(51.47 g, 0.31 mol), DTDL (0.14 g, 0.2 mmol), and acetone (80 mL) washeated with stirring to 55° C. After 2 hours, PCPSSIP (62.9 g, 0.09 molbased on a hydroxyl equivalent weight of 370 for the mixture) was added,and the mixture was heated for 2 additional hours at 55° C. A solutionof 3-aminopropyltriethoxysilane (20.6 g, 9.3 mmol) and butylamine (0.45g, 6.2 mmol) in acetone (69 mL) was added to the reaction mixture, whichwas maintained at 55° C. for an additional 15 minutes. Water (240 mL)was added to the reaction mixture over a 15 minute period with vigorousstirring and acetone was subsequently distilled from the mixture underreduced pressure to produce a dispersion of a silanol-terminatedpolyurethane-urea in water.

Example 4

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of 1,2-decanediol (22.05 g, 0.13 mol), 1,6-diisocyanatohexane(32.56 g, 0.19 mol), DTDL (0.09 g, 0.1 mmol), and acetone (51 mL) washeated with stirring to 55° C. After 2 hours, PCPSSIP (0.05 mol based ona hydroxyl equivalent weight of 370 for the mixture) was added, and themixture was heated for 2 additional hours at 55° C. A solution of3-aminopropyltriethoxysilane (1.97 g, 8.9 mmol) and butylamine (0.22 g,3.0 mmol) in acetone (45 mL) was added to the reaction mixture, whichwas maintained at 55° C. for an additional 15 minutes. Water (160 mL)was added to the reaction mixture over a 15 minute period with vigorousstirring and acetone was subsequently distilled from the mixture underreduced pressure to produce a dispersion of a silanol-terminatedpolyurethane-urea in water.

Example 5

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of 1,2-decanediol (24.28 g, 0.12 mol), 1,6-diisocyanatohexane(31.79 g, 0.19 mol), DTDL (0.08 g, 0.1 mmol), and acetone (52 mL) washeated with stirring to 55° C. After 2 hours, PCPSSIP (40.9 g, 0.06 molbased on a hydroxyl equivalent weight of 370 for the mixture) was added,and the mixture was heated for 2 additional hours at 55° C. A solutionof 3-aminopropyltriethoxysilane (1.12 g, 5.1 mmol) and butylamine (0.37g, 5.1 mmol) in acetone (45 mL) was added to the reaction mixture, whichwas maintained at 55° C. for an additional 15 minutes. Water (130 mL)was added to the reaction mixture over a 15 minute period with vigorousstirring and acetone was subsequently distilled from the mixture underreduced pressure to produce a dispersion of a silanol-terminatedpolyurethane-urea in water.

Example 6

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of 1,2-decanediol (27.88 g, 0.16 mol), 1,6-diisocyanatohexane(41.18 g, 0.24 mol), DTDL (0.11 g, 0.2 mmol), and acetone (64 mL) washeated with stirring to 55° C. After 2 hours, PCPSSIP (50.32 g, 0.07 molbased on a hydroxyl equivalent weight of 370 for the mixture) was added,and the mixture was heated for 2 additional hours at 55° C. A solutionof 3-aminopropyltriethoxysilane (2.15 g, 9.7 mmol) and butylamine (0.30g, 4.2 mmol) in acetone (55 mL) was added to the reaction mixture, whichwas maintained at 55° C. for an additional 15 minutes. Water (176 mL)was added to the reaction mixture over a 15 minute period with vigorousstirring and acetone was subsequently distilled from the mixture underreduced pressure to produce a dispersion of a silanol-terminatedpolyurethane-urea in water.

Example 7

Preparation of Silanol-terminated Polyurethane-urea in Water

A mixture of PCPSSIP (555 g, 0.75 mol based on a hydroxyl equivalentweight of 370 for the mixture), IPDI (190.1 g, 0.86 mol), DTDL (0.36 g,0.56 mmol), and acetone (400 g) was heated with stirring to 55° C. After8 hours, a solution of 3-aminopropyltriethoxysilane (45.3 g, 0.20 mol)in acetone (365 g) was added to the reaction mixture, which wasmaintained at 55° C. for an additional 15 minutes. Water (1700 g) wasadded to the reaction mixture over a 15 minute period with vigorousstirring and acetone was subsequently distilled from the mixture underreduced pressure to produce a dispersion (33% solids) of asilanol-terminated polyurethane-urea in water. MDSC analysis made of afilm of the dispersion indicated that the polymer had a T_(g) of −20° C.

Example 8

Preparation of a Carboxylated Polyurethane-urea Dispersion

A mixture of 2,2′-bis(hydroxymethyl)propionic acid (20.1 g, 0.150 mol),polycaprolactone diol (262 g, 0.50 mol), IPDI (159 g, 0.72 mol), MEK(237 g), and DTDL (0.30 g, 0.05 mmol) was heated at reflux for 5 hours,then left at room temperature for 72 hours. The mixture was then heatedat reflux for 6 more hours. An aliquot was removed for determination ofisocyanate equivalent weight as described in Example 29 of U.S. Pat. No.5,929,160, whose disclosure is incorporated herein in its entirety.Based on the found isocyanate equivalent weight of 3,607, a solution oftriethylamine (14.2 g, 0.141 mol) and 3-aminopropyltriethoxysilane (24.9g, 0.11 mol) in MEK (232 g) was added to the reaction mixture. Afterstirring for an additional 15 minutes, water (1350 g) was added to thesolution, and then the MEK was distilled from the mixture at reducedpressure to produce a 28% solids dispersion of the carboxylatedsilicon-containing polyurethane-urea in water.

Example 9

A 50/50 mixture of the dispersion from Example 4 and a dispersioncomprising AQ 1350 by the Eastman Chemical Co. as disclosed in WO98/38969 can be made.

Example 10

A 25/75 mixture of the dispersion from Example 6 and the dispersion fromExample 7 can be made.

2) Preparation of the Hair Styling Compositions

Four hair styling compositions were prepared using the components andamounts in weight percent listed hereafter. The testing was conducted onseveral models with one part of the head receiving a referencecomposition and the other side of the head receiving the testedcomposition. The compositions were applied to wet hair after shampooing.In some instances, the composition was rinsed off after application. Thehair was then dried, brushed, and evaluated.

Reference

AQ 1350 4% active material

Water qsp 100%

Formulation A:

Example 5 4% active material

Water qsp 100%

Formulation A imparted better hairstyling with better cosmeticproperties than the reference. The reshapable effect was found, whichwas equal to the reference.

Formulation B:

Example 6 4% active material

Water qsp 100%

Formulation B imparted better hairstyling and volume than the reference;however, the cosmetic properties and the reshapable effect, whilepresent, were not as good as the reference.

Formulation C:

Example 5 4% active material

Water qsp 100%

Formulation C, when rinsed, imparted better hairstyling with bettercosmetic properties than the reference; however, the reshapable effect,while present, was not as good as the reference.

Formulation D

Example 6 4% active material

Water qsp 100%

Formulation D, when rinsed, imparted better cosmetic properties than thereference; however, the hairstyling and the reshapable effect, whilepresent, were not as good as the reference.

What is claimed is:
 1. A reshapable hair styling composition comprisingat least one silicon-containing polycondensate chosen frompolyurethanes, polyureas, and polyurethane-ureas, wherein saidcomposition provides a reshapable effect.
 2. The composition accordingto claim 1, wherein said at least one silicon-containing polycondensateis in the form of a dispersion.
 3. The composition according to claim 2,wherein said at least one silicon-containing polycondensate is in theform of an aqueous dispersion.
 4. The composition according to claim 1,wherein said at least one silicon-containing polycondensate is in acosmetically acceptable vehicle.
 5. The composition according to claim1, wherein said at least one silicon-containing polycondensate has a Tgranging from about −100° C. to about 15° C.
 6. The composition accordingto claim 1, further comprising at least one additional polymer.
 7. Thecomposition according to claim 6, wherein said at least one additionalpolymer is chosen from anionic, cationic, amphoteric, and nonionicpolymers.
 8. The composition according to claim 1, further comprising atleast one conventional cosmetic constituent chosen from preservatives,perfumes, active hair care agents, plasticizers, anionic, cationic,amphoteric, and nonionic surfactants, hair conditioning agents, siliconefluids, fatty esters, fatty alcohol, long chain hydrocarbons,emollients, lubricants, penetrants, lanolin compounds, proteinhydrolysates, other protein derivatives, dyes, tins, bleaches, reducingagents, pH adjusting agents, sunscreens, and thickening agents.
 9. Acomposition according to claim 1, wherein said reshapable hair stylingcomposition is in the form of a spray, aerosol, mousse, gel, stick, mud,or lotion.
 10. A reshapable hair styling composition comprising at leastone silylated polycondensate chosen from polyurethanes, polyureas, andpolyurethane-ureas, wherein said composition provides a reshapableeffect.
 11. A composition according to claim 10, wherein said at leastone silylated polycondensate is the product of reactants comprising: (a)at least one isocyanate terminated polycondensate prepolymer; and (b) atleast one silyl containing component.
 12. The composition according toclaim 10, wherein said at least one silylated polycondensate is in theform of a dispersion.
 13. The composition according to claim 12, whereinsaid at least one silylated polycondensate is in the form of an aqueousdispersion.
 14. The composition according to claim 11, wherein said atleast one isocyanate terminated polycondensate polymer is the product ofreactants comprising: (i) at least one polyisocyanate and (ii) at leastone polyol.
 15. The composition according to claim 14, wherein, whereinsaid at least one polyisocyanate is chosen from diisocyanates.
 16. Thecomposition according to claim 14, wherein said at least onepolyisocyanate is chosen from dicyclohexylmethane 4,4′-diisocyanate,1,3-bis(isocyanatomethyl) cyclohexane,1,3-bis(1-isocyanato-1-methylethyl) benzene,3,5,5-trimethyl-1-isocyanato-3-isocyanatomethyl cyclohexane, m-phenylenediisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 4,4′-diisocyanato diphenylmethane, benzidinediisocyanate, naphthalene-1,5-diisocyanate, hexamethylene diisocyanate,tetramethylene diisocyanate, decamethylene diisocyanate, dodecamethylenediisocyanate, 4,4′,4″-triphenylmethane triisocyanate,polyphenylmethylene polyisocyanates that are produced by phosgenation ofaniline/formaldehyde condensation products containing up to about fouraromatic rings, dianisidine diisocyanate, xylene diisocyanate,bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)cyclohex-4-ene-1,2-dicarboxylate, and bis(2-isocyanatoethyl) carbonate.17. The composition according to claim 14, wherein said at least onepolyol is chosen from diols.
 18. The composition according to claim 14,wherein said at least one polyol is chosen from (a) lactone polyols andalkylene oxide adducts thereof, (b) polyester polyols, and alkyleneoxide adducts thereof, (c) polyoxyalkylene polyols, polyoxycycloalkylenepolyols, and alkylene oxide adducts thereof, and (d) polytetramethyleneglycols.
 19. The composition according to claim 14, wherein said atleast one polyol has a number average molecular weight ranging from 200to 5,000.
 20. The composition according to claim 11, wherein saidreactants further comprise at least one polyfunctional chain extender.21. The composition according to claim 20, wherein said at least onepolyfunctional chain extender is chosen from polyactive hydrogencompounds having a functionality of about 2 to about
 4. 22. Thecomposition according to claim 20, wherein said at least onepolyfunctional chain extender is chosen from water, ethylenediamine,1,6-diaminohexane, piperazine, tris(2-aminoethyl)amine, amine terminatedpolyethers, adipic acid dihydrazide, oxalic acid dihydrazide, ethyleneglycol, diethylene glycol, 1,4 butane diol, 1,8 octane diol,1,2-ethanedithiol, 1,4-butanedithiol, 2,2′-oxytris(ethane thiol),di-mercaptopropionate esters of poly(oxyethylene) diols, andtri-mercaptopropionate esters of poly(oxyethylene) triols.
 23. Thecomposition according to claim 11, wherein said reactants furthercomprise at least one hydrophilic component.
 24. The compositionaccording to claim 23, wherein said at least one hydrophilic componentis chosen from: (i) compounds containing an ionic group, (ii) compoundscontaining at least one moiety capable of forming an ionic group, and(iii) compounds containing a nonionic water soluble group.
 25. Thecomposition according to claim 24, wherein said at least one hydrophiliccomponent is a cationic compound having the following structure: R¹—N⁺(R²)[(CH₂CH₂O)_(n)H]₂X⁻ wherein R¹ is a group chosen from C₁ toC₁₈ alkyls, C₆ to C₁₈ aryls, and C₆ to C₁₈ arylalkyls optionallysubstituted in and/or on the chain by at least one atom chosen from N,O, and S atoms; R² is a group chosen from a hydrogen atom and C₁ to C₁₈alkyls; n is an integer ranging from about 1 to about 200; and X⁻ ischosen from halides, sulfates, methosulfates, ethosulfates, acetates,carbonates, and phosphates.
 26. The composition according to claim 24,wherein said at least one hydrophilic component is a compound of thestructure:

wherein M is a cation chosen from H, Na, K, Li, alkaline earth metals,and primary, secondary and tertiary ammonium cations; each R³ isindependently chosen from divalent aliphatic groups having an averagemolecular weight ranging from about 200 to about 600 comprising at leastone functional group chosen from ether and ester functional groups. 27.The composition according to claim 26, wherein said at least onefunctional group is chosen from: —CH₂CH₂—(OCH₂CH₂—)_(n)—,—CH(CH₃)CH₂—(OCH(CH₃)CH₂—)_(n)—, —(CH₂)₄—(O(CH₂)₄)_(n)—, and—(CH₂)_(m)CO—[O(CH₂)_(m)CO]_(n)— groups where m is an integer rangingfrom about 2 to about 5 and n is an integer ranging from about 2 toabout
 15. 28. The composition according to claim 23, wherein said atleast one hydrophilic component acts as a polyfunctional chain extender.29. The composition according to claim 10, wherein said at least onesilylated polycondensate is combined with an external surfactant. 30.The composition according to claim 11, wherein said at least one silylcontaining component is chosen from: H₂NCH₂CH₂CH₂Si(OC₂H₅)₃,HN(CH₂CH₂CH₂Si(OC₂H₅)₃)₂, HSCH₂CH₂CH₂Si(OCH₃)₃,HO(C₂H₄O)₃C₂H₄N(CH₃)(CH₂)₃Si(OC₄H₉)₃, H₂NCH₂C₆H₄CH₂CH₂Si(OCH₃)₃,HSCH₂CH₂CH₂Si(OCOCH₃)₃, H₂NCH₂CH₂CH₂Si(OCH₃)₃,

HN(CH₃)CH₂CH₂Si(OCH₃)₃, HSCH₂CH₂CH₂SiCH₃(OCH₃)₂,(HOC₂H₅)₂NC₃H₆Si(OCH₃)₃, H₂NCH₂CH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃, andOCNCH₂CH₂CH₂Si(OCH₃)₃.
 31. The composition according to claim 11,wherein said at least one silyl containing component acts as apolyfunctional chain extender.
 32. The composition according to claim10, wherein said at least one silylated polycondensate is in acosmetically acceptable vehicle.
 33. The composition according to claim11, wherein said reactants further comprise at least one chainterminator component.
 34. The composition according to claim 10, whereinsaid at least one silylated polycondensate has a Tg ranging from about−100° C. to about 15° C.
 35. The composition according to claim 10,further comprising at least one additional polymer.
 36. The compositionaccording to claim 35, wherein said at least one additional polymer ischosen from anionic, cationic, amphoteric, and nonionic polymers. 37.The composition according to claim 10, further comprising at least oneconventional cosmetic constituent chosen from preservatives, perfumes,active hair care agents, plasticizers, anionic, cationic, amphoteric,and nonionic surfactants, hair conditioning agents, silicone fluids,fatty esters, fatty alcohol, long chain hydrocarbons, emollients,lubricants, penetrants, lanolin compounds, protein hydrolysates, otherprotein derivatives, dyes, tins, bleaches, reducing agents, pH adjustingagents, sunscreens, and thickening agents.
 38. A composition accordingto claim 10, wherein said reshapable hair styling composition is in theform of a spray, aerosol, mousse, gel, stick, mud, or lotion.
 39. Areshapable hair styling composition comprising at least one siliconatedpolycondensate chosen from polyurethanes, polyureas, andpolyurethane-ureas, wherein said composition provides a reshapableeffect.
 40. The composition according to claim 39, wherein said at leastone siliconated polycondensate is in the form of a dispersion.
 41. Thecomposition according to claim 40, wherein said at least one siliconatedpolycondensate is in the form of an aqueous dispersion.
 42. Thecomposition according to claim 39, wherein said at least one siliconatedpolycondensate is in a cosmetically acceptable vehicle.
 43. Thecomposition according to claim 39, wherein said at least one siliconatedpolycondensate has a Tg ranging from about −100° C. to about 15° C. 44.The composition according to claim 39, further comprising at least oneadditional polymer.
 45. The composition according to claim 44, whereinsaid at least one additional polymer is chosen from anionic, cationic,amphoteric, and nonionic polymers.
 46. The composition according toclaim 39, further comprising at least one conventional cosmeticconstituent chosen from preservatives, perfumes, active hair careagents, plasticizers, anionic, cationic, amphoteric, and nonionicsurfactants, hair conditioning agents, silicone fluids, fatty esters,fatty alcohol, long chain hydrocarbons, emollients, lubricants,penetrants, lanolin compounds, protein hydrolysates, other proteinderivatives, dyes, tins, bleaches, reducing agents, pH adjusting agents,sunscreens, and thickening agents.
 47. A composition according to claim39, wherein said reshapable hair styling composition is in the form of aspray, aerosol, mousse, gel, stick, mud, or lotion.
 48. A reshapablehair styling composition comprising at least one polycondensate that isfunctionalized with at least one group chosen from hydrolyzed silylgroups and hydrolyzable silyl groups, wherein said at least onepolycondensate is the product of reactants comprising: (a) at least oneisocyanate terminated polycondensate prepolymer; (b) at least one silylcontaining component; and wherein said composition provides a reshapableeffect.
 49. The composition according to claim 48, wherein said at leastone polycondensate is in the form of a dispersion.
 50. The compositionaccording to claim 49, wherein said at least one polycondensate is inthe form of an aqueous dispersion.
 51. The composition according toclaim 48, wherein said at least one isocyanate terminated polycondensatepolymer is the product of reactants comprising: (i) at least onepolyisocyanate and (ii) at least one polyol.
 52. The compositionaccording to claim 51, wherein said at least one polyisocyanate ischosen from diisocyanates.
 53. The composition according to claim 51,wherein said at least one polyisocyanate is chosen fromdicyclohexylmethane 4,4′-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,3-bis(1-isocyanato-1-methylethyl) benzene,3,5,5-trimethyl-1-isocyanato-3-isocyanatomethyl cyclohexane, m-phenylenediisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 4,4′-diisocyanato diphenylmethane, benzidinediisocyanate, naphthalene-1,5-diisocyanate, hexamethylene diisocyanate,tetramethylene diisocyanate, decamethylene diisocyanate, dodecamethylenediisocyanate, 4,4′,4″-triphenylmethane triisocyanate,polyphenylmethylene polyisocyanates that are produced by phosgenation ofaniline/formaldehyde condensation products containing up to about fouraromatic rings, dianisidine diisocyanate, xylene diisocyanate,bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)cyclohex-4-ene-1,2-dicarboxylate, and bis(2-isocyanatoethyl) carbonate.54. The composition according to claim 51, wherein said at least onepolyol is chosen from diols.
 55. The composition according to claim 51,wherein said at least one polyol is chosen from (a) lactone polyols andalkylene oxide adducts thereof, (b) polyester polyols, and alkyleneoxide adducts thereof, (c) polyoxyalkylene polyols, polyoxycycloalkylenepolyols, and alkylene oxide adducts thereof, and (d) polytetramethyleneglycols.
 56. The composition according to claim 51, wherein said atleast one polyol has a number average molecular weight ranging from 200to 5,000.
 57. The composition according to claim 48, wherein saidreactants further comprise at least one polyfunctional chain extender.58. The composition according to claim 57, wherein said at least onepolyfunctional chain extender is chosen from polyactive hydrogencompounds having a functionality of about 2 to about
 4. 59. Thecomposition according to claim 57, wherein said at least onepolyfunctional chain extender is chosen from water, ethylenediamine,1,6-diaminohexane, piperazine, tris(2-aminoethyl)amine, amine terminatedpolyethers, adipic acid dihydrazide, oxalic acid dihydrazide, ethyleneglycol, diethylene glycol, 1,4 butane diol, 1,8 octane diol,1,2-ethanedithiol, 1,4-butanedithiol, 2,2′-oxytris(ethane thiol),di-mercaptopropionate esters of poly(oxyethylene) diols, andtri-mercaptopropionate esters of poly(oxyethylene) triols.
 60. Thecomposition according to claim 48, wherein said reactants furthercomprise at least one hydrophilic component.
 61. The compositionaccording to claim 60, wherein said at least one hydrophilic componentis chosen from: (i) compounds containing an ionic group, (ii) compoundscontaining at least one moiety capable of forming an ionic group, and(iii) compounds containing a nonionic water soluble group.
 62. Thecomposition according to claim 61, wherein said at least one hydrophiliccomponent is a cationic compound having the following structure:R¹—N⁺(R²)[(CH₂CH₂O)_(n)H]₂X⁻ wherein R¹ is a group chosen from C₁ to C₁₈alkyls, C₆ to C₁₈ aryls, and C₆ to C₁₈ arylalkyls optionally substitutedin and/or on the chain by at least one atom chosen from N, O, and Satoms; R² is a group chosen from a hydrogen atom and C₁ to C₁₈ alkyls; nis an integer ranging from about 1 to about 200; and X⁻ is chosen fromhalides, sulfates, methosulfates, ethosulfates, acetates, carbonates,and phosphates.
 63. The composition according to claim 61, wherein saidat least one hydrophilic component is a compound of the structure:

wherein M is a cation chosen from H, Na, K, Li, alkaline earth metals,and primary, secondary and tertiary ammonium cations; each R³ isindependently chosen from divalent aliphatic groups having an averagemolecular weight ranging from about 200 to about 600 comprising at leastone functional group chosen from ether and ester functional groups. 64.The composition according to claim 63, wherein said at least onefunctional group is chosen from: —CH₂CH₂—(OCH₂CH₂—)_(n)—,—CH(CH₃)CH₂—(OCH(CH₃)CH₂—)_(n)—, —(CH₂)₄—(O(CH₂)₄)_(n)—, and—(CH₂)_(m)CO—[O(CH₂)_(m)CO]_(n)— groups where m is an integer rangingfrom about 2 to about 5 and n is an integer ranging from about 2 toabout
 15. 65. The composition according to claim 60, wherein said atleast one hydrophilic component acts as a polyfunctional chain extender.66. The composition according to claim 48, wherein said at least onepolycondensate is combined with an external surfactant.
 67. Thecomposition according to claim 48, wherein said at least one silylcontaining component is chosen from: H₂NCH₂CH₂CH₂Si(OC₂H₅)₃,HN(CH₂CH₂CH₂Si(OC₂H₅)₃)₂, HSCH₂CH₂CH₂Si(OCH₃)₃,HO(C₂H₄O)₃C₂H₄N(CH₃)(CH₂)₃Si(OC₄H₉)₃, H₂NCH₂C₆H₄CH₂CH₂Si(OCH₃)₃,HSCH₂CH₂CH₂Si(OCOCH₃)₃, H₂NCH₂CH₂CH₂Si(OCH₃)₃,

HN(CH₃)CH₂CH₂Si(OCH₃)₃, HSCH₂CH₂CH₂SiCH₃(OCH₃)₂,(HOC₂H₅)₂NC₃H₆Si(OCH₃)₃, H₂NCH₂CH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃, andOCNCH₂CH₂CH₂Si(OCH₃)₃.
 68. The composition according to claim 48,wherein said at least one silyl containing component acts as apolyfunctional chain extender.
 69. The composition according to claim48, wherein said at least one polycondensate is in a cosmeticallyacceptable vehicle.
 70. The composition according to claim 48, whereinsaid reactants further comprise at least one chain terminator component.71. The composition according to claim 48, wherein said at least onepolycondensate has a Tg ranging from about −100° C. to about 15° C. 72.The composition according to claim 48, further comprising at least oneadditional polymer.
 73. The composition according to claim 72, whereinsaid at least one additional polymer is chosen from anionic, cationic,amphoteric, and nonionic polymers.
 74. The composition according toclaim 48, further comprising at least one conventional cosmeticconstituent chosen from preservatives, perfumes, active hair careagents, plasticizers, anionic, cationic, amphoteric, and nonionicsurfactants, hair conditioning agents, silicone fluids, fatty esters,fatty alcohol, long chain hydrocarbons, emollients, lubricants,penetrants, lanolin compounds, protein hydrolysates, other proteinderivatives, dyes, tins, bleaches, reducing agents, pH adjusting agents,sunscreens, and thickening agents.
 75. A composition according to claim48, wherein said reshapable hair styling composition is in the form of aspray, aerosol, mousse, gel, stick, mud, or lotion.
 76. An aerosoldevice comprising a vessel, which comprises: (1) an aerosol composition,which provides a reshapable effect and comprises a liquid phasecomprising at least one composition comprising at least onesilicon-containing polycondensate chosen from polyurethanes, polyureas,and polyurethane-ureas, wherein said composition provides a reshapableeffect, and a propellant, and (2) a dispenser.
 77. An aerosol devicecomprising a vessel, which comprises: (1) an aerosol composition, whichprovides a reshapable effect and comprises a liquid phase comprising atleast one composition comprising at least one silylated polycondensatechosen from polyurethanes, polyureas, and polyurethane-ureas, whereinsaid composition provides a reshapable effect, and a propellant, and (2)a dispenser.
 78. An aerosol device comprising a vessel, which comprises:(1) an aerosol composition, which provides a reshapable effect andcomprises a liquid phase comprising at least one composition comprisingat least one siliconated polycondensate chosen from polyurethanes,polyureas, and polyurethane-ureas, wherein said composition provides areshapable effect, and a propellant, and (2) a dispenser.
 79. An aerosoldevice comprising a vessel, which comprises: (1) an aerosol composition,which provides a reshapable effect and comprises a liquid phasecomprising at least one composition comprising at least onepolycondensate that is functionalized with at least one group chosenfrom hydrolyzed silyl groups and hydrolyzable silyl groups, wherein saidat least one polycondensate is the product of reactants comprising: (a)at least one isocyanate terminated polyurethane-urea prepolymer; and (b)at least one silyl containing component, wherein said compositionprovides a reshapable effect,  and a propellant, and (2) a dispenser.80. A method of cosmetically treating hair, comprising applying to thehair before, during, or after shaping of a hairstyle of said hair acomposition comprising at least one silicon-containing polycondensatechosen from polyurethanes, polyureas, and polyurethane-ureas, whereinsaid composition provides a reshapable effect.
 81. A method ofcosmetically treating hair, comprising applying to the hair before,during, or after shaping of a hairstyle of said hair a compositioncomprising at least one silylated polycondensate chosen frompolyurethanes, polyureas, and polyurethane-ureas, wherein saidcomposition provides a reshapable effect.
 82. A method of cosmeticallytreating hair, comprising applying to the hair before, during, or aftershaping of a hairstyle of said hair a composition comprising at leastone siliconated polycondensate chosen from polyurethanes, polyureas, andpolyurethane-ureas, wherein said composition provides a reshapableeffect.
 83. A method of cosmetically treating hair, comprising applyingto the hair before, during, or after shaping of a hairstyle of said haira composition comprising at least one polycondensate that isfunctionalized with at least one group chosen from hydrolyzed silylgroups and hydrolyzable silyl groups, wherein said at least onepolycondensate is the product of reactants comprising: (a) at least oneisocyanate terminated polyurethane-urea prepolymer; and (b) at least onesilyl containing component, wherein said composition provides areshapable effect.
 84. A method of reshaping hair, comprising: (1)applying to the hair before, during, or after the initial shaping of thehairstyle, a composition comprising at least one silicon-containingpolycondensate chosen from polyurethanes, polyureas, andpolyurethane-ureas, wherein said composition provides a reshapableeffect, and (2) thereafter reshaping the hairstyle at least once,wherein no additional composition or heat is added.
 85. A method ofreshaping hair, comprising: (1) applying to the hair before, during, orafter the initial shaping of the hairstyle, a composition comprising atleast one silylated polycondensate chosen from polyurethanes, polyureas,and polyurethane-ureas, wherein said composition provides a reshapableeffect, and (2) thereafter reshaping the hairstyle at least once,wherein no additional composition or heat is added.
 86. A method ofreshaping hair, comprising: (1) applying to the hair before, during, orafter the initial shaping of the hairstyle, a composition comprising atleast one siliconated polycondensate chosen from polyurethanes,polyureas, and polyurethane-ureas, wherein said composition provides areshapable effect, and (2) thereafter reshaping the hairstyle at leastonce, wherein no additional composition or heat is added.
 87. A methodof reshaping hair, comprising: (1) applying to the hair before, during,or after the initial shaping of the hairstyle, a composition comprisingat least one polycondensate that is functionalized with at least onegroup chosen from hydrolyzed silyl groups and hydrolyzable silyl groups,wherein said at least one polycondensate is the product of reactantscomprising: (a) at least one isocyanate terminated polyurethane-ureaprepolymer; and (b) at least one silyl containing component, whereinsaid composition provides a reshapable effect, and (2) thereafterreshaping the hairstyle at least once, wherein no additional compositionor heat is added.